An online method to determine chlorine stable isotope composition by continuous flow isotope ratio mass spectrometry (CF-IRMS) coupled with a Gasbench Ⅱ

An online method using continuous flow isotope ratio mass spectrometry （CF-IRMS） interfaced with a Gasbench Ⅱ was presented to determine chlorine stable isotope composition. Silver chloride （AgCl） was quantitatively derived from chloride by using silver nitrate （AgNO3）, and then was reacted with iodomethane （CH3Ⅰ） to produce methyl chloride （CH3Cl）. A GasBench Ⅱ equipped with a PoraPlot Q column was used to separate CH3Cl from any other gas species. Finally, chlorine stable isotope analysis was carried out on CH3Cl introduced to the IRMS in a helium stream via an active open split. The minimum amount of Cl used in this method is of the order of 1.4 μmol. Inter-laboratory and inter-technique comparisons show that the total uncertainty incorporating both the precision and accuracy of this method is better than 0.007%. Furthermore, ten seawaters sampled from different locations have a narrow δ37Cl value range from -0.008% to 0.010%, with a mean value of （0.000±0.006）%. This supports the assumption that any seawater can be representative of standard mean ocean chloride （SMOC） and used as an international reference material.

Carbon isotopic fractionation during vaporization of low molecular weight hydrocarbons(C6–C12)

Three series of laboratory vaporization experiments were conducted to investigate the carbon isotope fractionation of low molecular weight hydrocarbons（LMWHs）during their progressive vaporization.In addition to the analysis of a synthetic oil mixture,individual compounds were also studied either as pure single phases or mixed with soil.This allowed influences of mixing effects and diffusion though soil on the fractionation to be elucidated.The LMWHs volatilized in two broad behavior patterns that depended on their molecular weight and boiling point.Vaporization significantly enriched the ^13C present in the remaining components of the C6–C9 fraction,indicating that the vaporization is mainly kinetically controlled;the observed variations could be described with a Rayleigh fractionation model.In contrast,the heavier compounds（n-C10–n-C12）showed less mass loss and almost no significant isotopic fractionation during vaporization,indicating that the isotope characteristics remained sufficiently constant for these hydrocarbons to be used to identify the source of an oil sample,e.g.,the specific oil field or the origin of a spill.Furthermore,comparative studies suggested that matrix effects should be considered when the carbon isotope ratios of hydrocarbons are applied in the field.

Quantification,morphology and source of humic acid,kerogen and black carbon in offshore marine sediments from Xiamen Gulf,China

Three types of macromolecular organic matters （MOMs）, i.e. humic acid （HA）, kerogen＋black carbon （KB）, and black carbon （BC） were extracted from marine sediments of Xiamen Gulf, southeast of China. The chemical composition, morphological property and source of the three extractions were characterized by elemental analyzer/isotope ratio mass spectrometry （EA/IRMS） and scanning electron microscope （SEM）. The results showed that KB was the predominant fraction in MOMs, which accounted for 61.79%-89.15% of the total organic content （TOC）, while HA consisted less than 5%. The relative high contents of kerogen and BC, and low contents of HA in the samples indicated that anthropogenic input might be the major source of organic matter in marine sediments near the industrial regions. The characterization of SEM, not only revealed morphological properties of the three fractions, but also allowed a better understanding of the source of MOMs. The δ 13 C values of the three fractions suggested that materials from terrestrial C 3 plants were predominant. Furthermore, the anthropogenic activities, such as the discharge of sewage, coal and biomass combustion from industry nearby and agricultural practices within drainage basin of the Jiulong River, were remarkably contributed to the variations in δ 13 C values of MOMs in the offshore marine sediments.

A quantum cascade laser infrared spectrometer for CO_2 stable isotope analysis：Field implementation at a hydrocarbon contaminated site under bio-remediation

Real-time methods to monitor stable isotope ratios of CO_2 are needed to identify biogeochemical origins of CO_2 emissions from the soil–air interface. An isotope ratio infra-red spectrometer（IRIS） has been developed to measure CO_2 mixing ratio with δ~13C isotopic signature, in addition to mixing ratios of other greenhouse gases（CH_4, N2_O）. The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ~13C of CO_2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO_2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ~13C of the CO_2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO_2 emissions have been measured with an isotopic signature δ~13C suggesting that CO_2 comes from petroleum hydrocarbon biodegradation.This first field implementation shows that rapid and accurate measurement of isotopic signature of CO_2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO_2 efflux and is promising as a monitoring tool for aerobic bio-treatment.

Developing an authentication approach using SPME-GC-IRMS based on compound-specific δ^(13)C analysis of six typical volatiles in wine

An analytical method using gas chromatography isotope ratio mass spectrometry(GC-IRMS)combined with solid phase micro-extraction(SPME)was developed to measure the 613C values of six typical volatiles commonly occurring in wine(isoamyl acetate,2-octanone,limonene,2-phenylethanol,ethyl octanoate and ethyl decanoate)for the first time.SPME selected with a divinylbenzene/carboxen/polydimethylsiloxane fiber was combined with the GC-IRMS for pretreatment optimization.The optimized SPME parameters of extraction time,extraction temperature and salt concentration were 40 min,40℃ and 10%,respectively.The 613C values measured by SPME-GC-IRMS were in good agreement with those measured via elemental analyzer(EA)-IRMS and GC-IRMS.The differences range from 0.02‰to 0.44‰ with EA-IRMS and from 0 to 0.28‰ with GC-IRMS,indicating the high accuracy of the method.This newly established method measured the precision within 0.30‰ and was successfully validated to discriminate imported real wine samples with identical label but amazing price differences from different importers.